JPH11166011A - Catalyst component for alpha-olefin polymerization, catalyst, and production of alpha-olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst component having high polymerization activity per transition metal compound and capable of obtaining a polymer having a large molecular weight by combining a specific metallocene-based transition metal compound with an ion-exchangeable layered silicicate. SOLUTION: This catalyst component is obtained by combining (i) a metallocene-based transition metal compound of the formula (CpR<1> )2 MX<1> X<2> (Cp is a cyclopentadienyl; R<1> is a silicon-containing group having secondary or tertiary silicon directly bonded to Cp ring or a secondary or tertiary amino or the like; X<1> and X<2> are each a halogen, H, amide, etc.), with (ii) an ion exchangeable layered silicate. This catalyst for α-olefin polymerization is obtained by combining the catalyst component with (B) an organic aluminum compound of the formula R<2> 3 AlX<3> 3-a [R<2> is a 1-20C hydrocarbon; X<3> is a halogen, H, etc.; 0<(a)<=3].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst component for olefin polymerization, a catalyst, and a method for obtaining an olefin polymer in a high yield by using the catalyst. More specifically, the present invention can be applied to solution polymerization, high-pressure polymerization, slurry polymerization, and gas-phase polymerization, and particularly when applied to slurry polymerization and gas-phase polymerization, an olefin polymer having a high molecular weight. The present invention relates to an olefin polymerization catalyst capable of producing olefins and a method for obtaining an olefin polymer in a high yield by using the catalyst.

[0002]

2. Description of the Related Art In producing an olefin polymer by polymerizing an olefin, a method using a catalyst comprising (1) a metallocene compound and (2) an aluminoxane has been proposed (Japanese Patent Application Laid-Open No. 58-119309, JP-A-2-167307). A polymerization method using these catalysts is based on a conventional Ziegler-based compound comprising a titanium compound or a vanadium compound and an organoaluminum compound.
Compared with the method using a Natta catalyst, a polymer having a very high polymerization activity per transition metal and a sharp molecular weight distribution and a sharp composition distribution can be obtained.

However, in order to industrially obtain sufficient polymerization activity using these catalysts, a large amount of aluminoxane is required, so that the polymerization activity per aluminum is low, which is not only uneconomical, but also produces It was necessary to remove catalyst residues from the polymer.

On the other hand, there has been proposed a method of polymerizing an olefin with a catalyst in which one or both of the metallocene complex and aluminoxane are supported on an inorganic oxide such as silica or alumina (Japanese Patent Application Laid-Open No. 61-108610,
JP-A-60-135408, JP-A-61-296008, JP-A-3-74412, JP-A-3-74415
No.). There has also been proposed a method of polymerizing an olefin using a catalyst system in which one or both of a metallocene compound and an organoaluminum compound is supported on an inorganic oxide or an organic substance such as silica or alumina (Japanese Patent Application Laid-Open No. 1-1990).
Nos. 101303, 1-207303, and 3
JP-A-234709, JP-A-3-501869). Further, a method of prepolymerizing these supported catalysts has also been proposed (Japanese Patent Application Laid-Open No. 3-234710).

[0005] However, even in these proposed methods, the polymerization activity per aluminum was still not sufficient, and the amount of catalyst residue in the product was not negligible. As a solution to these problems,
A catalyst comprising an ion-exchangeable layered compound or an inorganic silicate, an organoaluminum and a metallocene compound, and a catalyst obtained by prepolymerizing the same have been proposed (Japanese Patent Laid-Open Publication No. Hei 5 (1994)).
-29522).

Although these catalysts have sufficient polymerization activity per transition metal or aluminum, it has been found that hydrogen is generated during polymerization and the generated hydrogen reduces the molecular weight of the polymer. In order to obtain, it is necessary to control a very small amount of hydrogen or to take special measures such as removing generated hydrogen.

On the other hand, in a catalyst comprising a metallocene compound and an aluminoxane, at least one of the ligands of the metallocene compound is a cyclopentadienyl ligand having two different substituents. A method for obtaining an olefin polymer having a narrow molecular weight distribution has been proposed (JP-A-5-148317). However, even when this catalyst was used, the molecular weight of the polymer obtained was not always sufficient.

[0008]

DISCLOSURE OF THE INVENTION The present invention relates to a catalyst component and a catalyst for α-olefin polymerization which have a high polymerization activity per transition metal compound as a catalyst component and can obtain a polymer having a large molecular weight. An object of the present invention is to provide a method for polymerizing an α-olefin using

[0009]

Means for Solving the Problems The present inventors have conducted studies to solve the above-mentioned problems, and as a result, have found that a metallocene transition metal compound having a branched structure substituent is added to an ion-exchange layered silicate. The present catalyst system was found to have a sufficiently high polymerization activity per transition metal and aluminum and to produce a polymer having a high molecular weight by supporting the catalyst. That is, the present invention provides an α-olefin polymerization catalyst component obtained by combining the following components [A] and [B]. [A] A metallocene transition metal compound.

[0010]

Embedded image (CpR ¹ ) ₂ MX ¹ X ² [1]

(In the formula [1], Cp represents a cyclopentadienyl group, and R ¹ represents a silicon-containing group having a secondary or tertiary silicon atom directly bonded to a Cp ring, a secondary or tertiary amino group. At least one of the carbon atoms of the hydrocarbon group
One of which is not bonded to a hydrogen atom or is bonded to one hydrogen atom, a hydrocarbon group having 3 to 20 carbon atoms, or at least one of the carbon atoms is not bonded to a hydrogen atom or is bonded to one hydrogen atom 1 to 20 carbon atoms bonded
Represents a halogen-containing hydrocarbon group. M is titanium, zirconium or hafnium; X ¹ and X ² each independently represent a halogen atom, a hydrogen atom,
20 hydrocarbon groups, alkoxy groups, aryloxy groups,
It represents an amide group or a trifluoromethanesulfonic acid group. )

[B] Ion-exchangeable layered silicate. The present invention also provides an α-olefin polymerization catalyst obtained by combining the above-mentioned catalyst component with the following component [C], and a method for producing an α-olefin polymer using the polymerization catalyst. is there. [C] An organoaluminum compound represented by the following formula [2].

[0013]

Embedded image _{^{[C] R 2 a AlX 3}} 3-a [2]

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The component [A] metallocene transition metal compound used in the catalyst of the present invention is an organometallic compound comprising a substituted cyclopentadienyl ligand and titanium, zirconium or hafnium. Preferred as such a metallocene transition metal compound is a compound represented by the following general formula [1].

[0015]

Embedded image (CpR ¹ ) ₂ MX ¹ X ² [1]

(In the formula [1], Cp represents a cyclopentadienyl group, and R ¹ represents a silicon-containing group having a secondary or tertiary silicon atom directly bonded to a Cp ring, a secondary or tertiary amino group. At least one of the carbon atoms of the hydrocarbon group
One of which is not bonded to a hydrogen atom or is bonded to one hydrogen atom, a hydrocarbon group having 3 to 20 carbon atoms, or at least one of the carbon atoms is not bonded to a hydrogen atom or is bonded to one hydrogen atom 1 to 20 carbon atoms bonded
Represents a halogen-containing hydrocarbon group. M is titanium, zirconium or hafnium; X ¹ and X ² each independently represent a halogen atom, a hydrogen atom,
20 hydrocarbon groups, alkoxy groups, aryloxy groups,
It represents an amide group or a trifluoromethanesulfonic acid group. )

In the present invention, 2 is directly bonded to the Cp ring.
The silicon-containing compound having a tertiary or tertiary silicon atom means a substituent having the following constituent parts.

[0018]

Embedded image

A secondary amino group and a tertiary amino group mean substituents having the following constituents.

[0020]

Embedded image

The hydrocarbon group has a hydrocarbon group in which at least one of the carbon atoms is not bonded to hydrogen or bonded to one hydrogen atom, that is, a tertiary or quaternary carbon atom, Branched hydrocarbons can be used. The position of the branch is arbitrary, and a branch at any position from the α position to the ω-1 position is used. Further, a branched hydrocarbon having a secondary or tertiary carbon atom directly bonded to the Cp ring can also be used. Such a branched hydrocarbon means a substituent having the following structural unit.

[0022]

Embedded image

As the hydrocarbon group, there can be used a hydrocarbon group in which a carbon which is directly bonded to Cp and forms a part of the ring or a hydrocarbon group containing halogen. Such a substituent is exemplified by a hydrocarbon group. And a substituent having the following structure.

[0024]

Embedded image

Specifically, silicon-containing groups such as trimethylsilyl, triethylsilyl, and triphenylsilyl groups;
Amino groups such as dimethylamino group, diethylamino group, diisopropylamino group, diphenylamino group, dicyclohexylamino group, pyridyl group and indolyl group, i-propyl group, i-butyl group, s-butyl group, t-butyl group, i -Pentyl group, neo-pentyl group, t-bentyl group, cyclopentyl group, cyclohexyl group, phenyl group, hydrocarbon group having 1 to 20 carbon atoms such as 4-methylphenyl group, or difluoromethyl group, trifluoromethyl group, Examples thereof include a halogen-containing hydrocarbon group having 1 to 20 carbon atoms such as a 2,2,2-trifluoroethyl group, a pentafluorophenyl group, a 4-fluorophenyl group, and a 2-fluorophenyl group. Of these, particularly preferred are a 1-propyl group, a cyclohexyl group and a cyclopentyl group.

X ¹ and X ² each independently represent a hydrogen atom, a halogen such as chlorine or bromine, a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
C 1-20 such as butyl group, t-butyl group, n-pentyl, n-hexyl group, cyclohexyl group, n-heptyl group, n-nonyl group, n-decyl group, phenyl group and 4-methylphenyl group Hydrocarbon group, methoxy group, ethoxy group, propoxy group, alkoxy group such as butoxy group, phenoxy group, 4-methylphenoxy group, aryloxy group such as pentamethylphenoxy group, dimethylamide group,
Amide group such as diethylamide group, diisopropylamide group, diphenylamide group, dicyclohexylamide group,
Shows trifluoromethanesulfonic acid and the like. Among them, chlorine, hydrogen atom, methyl group, dimethylamide group, diethylamide group, and trifluoromethanesulfonic acid group are preferable.

Specific examples of the metallocene transition metal compound represented by the above formula [1] when M is zirconium include bis (i-propylcyclopentadienyl) zirconium dichloride and bis (i-butyl). Cyclopentadienyl) zirconium dichloride, bis (s-butylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, bis (i-pentylcyclopentadienyl) zirconium dichloride, bis (neo) −
Pentylcyclopentadienyl) zirconium dichloride, bis (t-pentylcyclopentadienyl) zirconium dichloride, bis (cyclopentylcyclopentadienyl) zirconium dichloride, bis (cyclohexylcyclopentadienyl) zirconium dichloride,
Bis (phenylcyclopentadienyl) zirconium dichloride, bis (4-methylphenylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (diethylaminocyclopentadienyl) zirconium dichloride, bis (tri Fluoromethylcyclopentadienyl) zirconium dichloride, bis (i-propylcyclopentadienyl) zirconium dimethyl, bis (i-butylcyclopentadienyl) zirconium dimethyl, bis (s-butylcyclopentadienyl) zirconium dimethyl, bis (T-butylcyclopentadienyl) zirconium dimethyl, bis (i-pentylcyclopentadienyl) zirconium dimethyl, bis (neo
-Pentylcyclopentadienyl) zirconium dimethyl, bis (t-pentylcyclopentadienyl) zirconium dimethyl, bis (cyclopentylcyclopentadienyl) zirconium dimethyl, bis (cyclohexylcyclopentadienyl) zirconium dimethyl, bis (phenylcyclopenta Dienyl) zirconium dimethyl, bis (4-methylphenylcyclopentadienyl)
Zirconium dimethyl, bis (trimethylsilylcyclopentadienyl) zirconium dimethyl, bis (diethylaminocyclopentadienyl) zirconium dimethyl, bis (trifluoromethylcyclopentadienyl)
Zirconium dimethyl, bis (i-propylcyclopentadienyl) zirconium methyl chloride, bis (i-
Butylcyclopentadienyl) zirconium methyl chloride, bis (s-butylcyclopentadienyl) zirconium methyl chloride, bis (t-butylcyclopentadienyl) zirconium methyl chloride, bis (i-pentylcyclopentadienyl) zirconium methyl Chloride, bis (neo-pentylcyclopentadienyl)
Zirconium methyl chloride, bis (t-pentylcyclopentadienyl) zirconium methyl chloride, bis (cyclopentylcyclopentadienyl) zirconium methyl chloride, bis (cyclohexylcyclopentadienyl) zirconium methyl chloride, bis (phenylcyclopentadienyl) Zirconium methyl chloride,
Bis (4-methylphenylcyclopentadienyl) zirconium methyl chloride, bis (trimethylsilylcyclopentadienyl) zirconium methyl chloride, bis (diethylaminocyclopentadienyl) zirconium methyl chloride, bis (trifluoromethylcyclopentadienyl) zirconium Methyl chloride, bis (i-
Propylcyclopentadienyl) zirconium diethyl, bis (i-butylcyclopentadienyl) zirconium diethyl, bis (s-butylcyclopentadienyl) zirconium diethyl, bis (t-butylcyclopentadienyl) zirconium diethyl, bis ( i-pentylcyclopentadienyl) zirconium diethyl, bis (neo-pentylcyclopentadienyl) zirconium diethyl, bis (t-pentylcyclopentadienyl) zirconium diethyl, bis (cyclopentylcyclopentadienyl) zirconium diethyl, bis ( Cyclohexylcyclopentadienyl) zirconium diethyl, bis (phenylcyclopentadienyl) zirconium diethyl, bis (4-methylphenylcyclopentadienyl) zirconium Ethyl, bis (trimethylsilylcyclopentadienyl) zirconium diethyl, bis (diethylaminocyclopentadienyl) zirconium diethyl, bis (trifluoromethylcyclopentadienyl) zirconium diethyl, bis (i-propylcyclopentadienyl) zirconium diisobutyl, Bis (i-butylcyclopentadienyl) zirconium diisobutyl, bis (s-butylcyclopentadienyl) zirconium diisobutyl, bis (t-butylcyclopentadienyl) zirconium diisobutyl, bis (i-pentylcyclopentadienyl) zirconium Diisobutyl, bis (neo-pentylcyclopentadienyl) zirconium diisobutyl, bis (t-pentylcyclopentadienyl) zirconium diisobutyl Bis (cyclopentylmethyl cyclopentadienyl) zirconium diisobutyl, bis (cyclohexyl cyclopentadienyl)
Zirconium diisobutyl, bis (phenylcyclopentadienyl) zirconium diisobutyl, bis (4-methylphenylcyclopentadienyl) zirconium diisobutyl, bis (trimethylsilylcyclopentadienyl) zirconium diisobutyl, bis (diethylaminocyclopentadienyl) zirconium diisobutyl, Bis (trifluoromethylcyclopentadienyl) zirconium isobutyl, bis (i-propylcyclopentadienyl) zirconium chloride monohydride, bis (i-butylcyclopentadienyl) zirconium chloride monohydride, bis (s-butylcyclo) (Pentadienyl) zirconium chloride monohydride, bis (t-butylcyclopentadienyl) zirconium chloride monohydride Id, bis (i-pentylcyclopentadienyl) zirconium chloride monohydride, bis (neo-pentylcyclopentadienyl) zirconium chloride monohydride, bis (t-pentylcyclopentadienyl) zirconium chloride monohydride, bis (cyclopentyl) (Cyclopentadienyl) zirconium chloride monohydride, bis (cyclohexylcyclopentadienyl) zirconium chloride monohydride, bis (4-methylphenylcyclopentadienyl) zirconium chloride monohydride, bis (trimethylsilylcyclopentadienyl) zirconium chloride mono Hydride, bis (diethylaminocyclopentadienyl) zirconium chloride monohydride, bis (triflu B methylcyclopentadienyl) zirconium dichloride monohydride, bis (i-propyl cyclopentadienyl) zirconium dihydride, bis (i-butylcyclopentadienyl) zirconium dihydride, bis (s-
Butylcyclopentadienyl) zirconium dihydride, bis (t-butylcyclopentadienyl) zirconium dihydride, bis (i-pentylcyclopentadienyl) zirconium dihydride, bis (ne
o-pentylcyclopentadienyl) zirconium dihydride, bis (t-pentylcyclopentadienyl) zirconium dihydride, bis (cyclopentylcyclopentadienyl) zirconium dihydride, bis (cyclohexylcyclopentadienyl) zirconium dihydride, Bis (phenylcyclopentadienyl) zirconium dihydride, bis (4-methylphenylcyclopentadienyl) zirconium dihydride, bis (trimethylsilylcyclopentadienyl) zirconium dihydride, bis (diethylaminocyclopentadienyl) zirconium dihydride , Bis (trifluoromethylcyclopentadienyl)
Zirconium dihydride, bis (i-propylcyclopentadienyl) zirconium dimethoxide, bis (i-butylcyclopentadienyl) zirconium dimethoxide, bis (s-butylcyclopentadienyl) zirconium dimethoxide, bis (t- Butylcyclopentadienyl) zirconium dimethoxide, bis (i-pentylcyclopentadienyl) zirconium dimethoxide, bis (neo-pentylcyclopentadienyl) zirconium dimethoxide, bis (t-pentylcyclopentadienyl) zirconium dimethoxy , Bis (cyclopentylcyclopentadienyl) zirconium dimethoxide, bis (cyclohexylcyclopentadienyl)
Zirconium dimethoxide, bis (phenylcyclopentadienyl) zirconium dimethoxide, bis (4-methylphenylcyclopentadienyl) zirconium dimethoxide, bis (trimethylsilylcyclopentadienyl) zirconium dimethoxide, bis (diethylaminocyclopentadienyl) ) Zirconium dimethoxide, bis (trifluoromethylcyclopentadienyl) zirconium dimethoxide, bis (i-propylcyclopentadienyl) zirconium bis (dimethylamide), bis (i-butylcyclopentadienyl) zirconium bis (dimethyl) Amide), bis (s-butylcyclopentadienyl) zirconium bis (dimethylamide), bis (t-butylcyclopentadienyl) zirconium bis (dimethylamide) Bis (i-pentylcyclopentadienyl) zirconium bis (dimethylamide), bis (neo-pentylcyclopentadienyl) zirconium bis (dimethylamide), bis (t-pentylcyclopentadienyl) zirconium bis (dimethylamide) , Bis (cyclopentylcyclopentadienyl) zirconium bis (dimethylamide), bis (cyclohexylcyclopentadienyl) zirconium bis (dimethylamide), bis (phenylcyclopentadienyl) zirconium bis (dimethylamide), bis (4-dimethylamide) Methylphenylcyclopentadienyl) zirconium bis (dimethylamide), bis (trimethylsilylcyclopentadienyl) zirconium bis (dimethylamide), bis (diethylaminocyclopentadienyl) Ruconium bis (dimethylamide), bis (trifluoromethylcyclopentadienyl) zirconium bis (dimethylamide), bis (i-propylcyclopentadienyl) zirconium bis (diethylamide), bis (i-butylcyclopentadienyl) zirconium Bis (diethylamide), bis (s-butylcyclopentadienyl) zirconium bis (diethylamide), bis (t-butylcyclopentadienyl) zirconium bis (diethylamide), bis (i-pentylcyclopentadienyl) zirconium bis ( Diethylamide), bis (neo-pentylcyclopentadienyl) zirconium bis (diethylamide), bis (t-pentylcyclopentadienyl) zirconium bis (diethylamide), bis (cyclopentyl) Cyclopentadienyl) zirconium bis (diethylamide), bis (cyclohexylcyclopentadienyl) zirconium bis (diethylamide), bis (phenylcyclopentadienyl) zirconium bis (diethylamide), bis (4-methylphenylcyclopentadienyl) Zirconium bis (diethylamide), bis (trimethylsilylcyclopentadienyl)
Zirconium bis (diethylamide), bis (diethylaminocyclopentadienyl) zirconium bis (diethylamide), bis (trifluoromethylcyclopentadienyl) zirconium bis, bis (i-propylcyclopentadienyl) zirconium diethylamide monochloride, bis ( i-butylcyclopentadienyl) zirconium diethylamide monochloride, bis (s-butylcyclopentadienyl) zirconium diethylamide monochloride, bis (t-butylcyclopentadienyl) zirconium diethylamide monochloride, bis (i-pentylcyclopenta Dienyl) zirconium diethylamide monochloride, bis (neo-pentylcyclopentadienyl) zirconium diethylamide monochloride, bis (t- Down chill cyclopentadienyl)
Zirconium diethylamide monochloride, bis (cyclohexylcyclopentadienyl) zirconium diethylamide monochloride, bis (phenylcyclopentadienyl) zirconium diethylamide monochloride, bis (4-methylphenylcyclopentadienyl) zirconium diethylamide monochloride, bis (trimethylsilyl) Cyclopentadienyl) zirconium diethylamide monochloride, bis (diethylaminocyclopentadienyl) zirconium diethylamide monochloride,
Bis (trifluoromethylcyclopentadienyl) zirconium diethylamide monochloride.

Of these, bis (i-propylcyclopentadienyl) zirconium dichloride, bis (s-butylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, bis (cyclopentyl) Cyclopentadienyl) zirconium dichloride, bis (cyclohexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (i-propylsilylcyclopentadienyl) zirconium dimethyl, bis (s-
Butylcyclopentadienyl) zirconium dimethyl,
Bis (t-butylcyclopentadienyl) zirconium dimethyl, bis (cyclopentylcyclopentadienyl) zirconium dimethyl, bis (cyclohexylcyclopentadienyl) zirconium dimethyl, bis (trimethylsilylcyclopentadienyl) zirconium dimethyl, bis (i- Propylcyclopentadienyl) zirconium bis (diethylamide), bis (s-butylcyclopentadienyl) zirconium bis (diethylamide), bis (t-butylcyclopentadienyl) zirconium bis (diethylamide), bis (cyclopentylcyclopentadiethyl) ) Zirconium bis (diethylamide), bis (cyclohexylcyclopentadienyl)
Zirconium bis (diethylamide) and bis (trimethylsilylcyclopentadienyl) zirconium bis (diethylamide) are preferred.

Further, as the metatheron-based transition metal compound which is the component [A] of the present catalyst, M of the formula [1] is titanium,
Specific examples of the case of hafnium include titanium and hafnium compounds of the above zirconium compounds.

As the component [B] of the present catalyst, an ion-exchange layered silicate is used. An ion-exchangeable phyllosilicate is a silicate compound having a crystal structure in which a plate-like structure formed by covalent bonds or the like is stacked in parallel with weak ionic bonding force or the like, and the ions contained therein are exchangeable. . Ion-exchanged layered silicates are naturally produced mainly as a main component of clay minerals, but these ion-exchanged layered silicates are not particularly limited to natural ones and may be artificially synthesized. .

Specific examples of the ion-exchangeable layered silicate include kaolins such as dickite, nacrite, kaolinite, anoxite, metahaloysite, and halloysite, serpentine groups such as chrysotile, risaldite, antigolite, and montmorillonite. Zaukonite, beidellite, nontronite, saponite, bentrite,
Smectites such as hectorite and stevensite,
Vermiculite, vermiculite, illite,
Examples include mica tribes such as sericite and chlorite, attapulgite, sepiolite, palygorskite, pyrophyllite, talc, chlorite, allophane, and imogolite. These may form a mixed layer.

Among these, montmorillonite, saukonite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite,
Smectites such as teniolite and mica, vermiculites and mica are preferred. These may be used as such without any particular treatment, ball milling, sieving, hydrochloric acid, sulfuric acid, inorganic acids such as phosphoric acid, formic acid, acetic acid,
It may be used after a treatment such as an acid treatment by contact with an organic acid such as benzoic acid. When used alone,
Mixtures of more than one species may be used.

The above-mentioned ion-exchange layered silicate can substitute and exchange cations between layers or the like with other cations by utilizing its ion-exchange properties. Specifically, an alkali metal such as Na ⁺ and Li ⁺ existing between the layers is exchanged with a salt having another cation, an acid, an alkali, an organic compound, or the like. The ion exchange method is not particularly limited, and a general method can be employed. One example is salts,
This is performed by adding and dispersing the ion-exchange layered silicate to an aqueous solution of an acid, an alkali or an organic compound and stirring the mixture for a desired time. At this time, the ion exchange amount can be controlled to a desired value by appropriately selecting the concentration, temperature, and the like of salts, acids, alkalis, or organic compounds. As such salts, acids, alkalis or organic compounds, specifically, inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid;
Organic acids such as acetic acid and oxalic acid, and polyacids typified by heteropolyacid can be exemplified. In these cases, H ⁺ is exchanged between layers. Further, after ion exchange with ammonium ions such as ammonium chloride and ammonium sulfate, H ⁺ can be introduced between the layers by heat treatment or the like. In addition, salts composed of a cation containing at least one kind of atom selected from the group consisting of Group 2 to 14 atoms and at least one kind of anion can be used. Examples of such salts include magnesium and aluminum. , Titanium, vanadium, chromium, manganese, iron,
Examples include chlorides, bromides, iodides, sulfates, nitrates, chlorates, and perchlorates of cobalt, nickel, copper, zinc, zirconium, tin and the like. In this case, a cation containing at least one atom selected from the group consisting of Group 2 to 14 atoms is introduced between the layers. Examples of the ion-exchangeable organic compound include monobutylammonium ion, dibutylammonium ion, tributylammonium ion, tetrabutylammonium ion, anilinium ion, dimethylanilinium ion, tetraphenylphosphonium ion, and tetrabutylphosphonium ion. An organic compound having an ammonium ion, a phosphonium ion, or the like having one hydrocarbon group can be given. Further, organometallic compounds such as porphyrin and crown ether complex salts can be introduced. Further, by appropriately selecting the salt treatment conditions, the atoms in the layer structure can be exchanged.

These ion-exchangeable phyllosilicates can be changed in chemical composition by, for example, elution of cations from the layer structure, etc., in addition to replacing ions existing between layers with protons by acid treatment. . In such an acid treatment, a desired acid-treated ion-exchange layered silicate can be obtained by appropriately selecting treatment conditions (acid concentration, temperature) and the kind of acid. The acid used in such an acid treatment is not particularly limited, but preferably hydrochloric acid, sulfuric acid,
Nitric acid, acetic acid or oxalic acid. These acids may be used alone or in combination of two or more, and may be used in combination with the salt treatment.

When these ion-exchangeable layered silicates are used in the present catalyst, they may be used in any shape in accordance with the polymerization apparatus to be used, but are applicable to a gas phase polymerization method, a slurry polymerization method and the like. In this case, the average particle size is from 5 μm to 1
The use of granulated particles having a particle size of 00 μm is advantageous in terms of process operation since the bulk density of the catalyst and the obtained polymer can be increased.

These ion-exchange layered silicates are
It is preferable to dry before reacting with the metallocene complex. In the present invention, a catalyst can be obtained by combining, for example, a component [C] represented by the following formula [2] with a catalyst component obtained by combining the components [A] and [B].

[0037]

Embedded image _{^{[C] R 2 a AlX 3}} 3-a [2]

(In the formula [2], R ² has 1 to ² carbon atoms.
A hydrocarbon group of 0, X ³ represents a halogen atom, a hydrogen atom, an alkoxy group or an amide group, and a is a number satisfying 0 <a ≦ 3). Specific examples of the component [C] include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, and tri-n-hexylaluminum, and alkylaluminums such as diethylaluminum hydride and diisobutylaluminum hydride. Hydride, diethyl aluminum chloride, halogen-containing alkyl aluminum such as diisobutyl aluminum chloride, diethyl aluminum methoxide,
Examples thereof include alkyl aluminum alkoxides such as diisobutyl aluminum methoxide, and alkyl aluminum amides such as diethyl aluminum (diethyl amide) and diisobutyl aluminum (diethyl amide). These aluminum compounds may be used alone,
For example, two or more kinds such as a mixture of triethylaluminum and triisobutylaluminum, or a mixture of a trialkylaluminum and a halogen-containing alkylaluminum may be used.

The method for producing the catalyst is not particularly limited. For example, the catalyst can be produced by the following method. In an inert gas, a previously dried salt- or acid-treated ion-exchanged layered silicate is suspended in a hydrocarbon solvent, and a metallocene complex-dissolved hydrocarbon solution and, if necessary, an organoaluminum compound are added thereto. In addition, it is obtained by processing for a predetermined time.

In the present invention, the components [A] to [C] may be preliminarily polymerized by contacting them with an α-olefin or an aromatic vinyl monomer in advance, that is, the prepolymerized one may be used as a catalyst. The prepolymerization is usually carried out with ethylene, but if necessary, other olefins such as propylene, 1-butene, 4-methyl-1-
Α-olefins such as pentene and 3-methyl-1-pentene; aromatic vinyl monomers such as styrene and α-methylstyrene; and mixtures thereof can be used.

When the catalyst of the present invention is used as a prepolymerized catalyst, a prepolymerized polymer is present in the catalyst. The amount of the prepolymerized polymer present in the catalyst is 0.01 to 1000 g, preferably 0.1 g, per 1 g of the component [B] used, that is, 1 g of the ion-exchange layered silicate.
It is 1 g to 100 g, more preferably 1 g to 50 g.

Examples of the solvent used for contacting the ion-exchange layered silicate with the metallocene transition metal compound include inert hydrocarbons, specifically, chain hydrocarbons such as pentane, hexane and heptane, benzene, toluene and xylene. Is preferred. The contact temperature is not particularly limited, but may be from -20 ° C to 15 ° C.
It is preferably carried out between 0 ° C. The amount of the metallocene transition metal compound used for the component [B], which is an ion-exchange layered silicate, that is, the amount of the component [A] is appropriately selected, but is preferably 1 μmol per 1 g of the component [B]. ~
Used in an amount of 1000 μmol.

The method of prepolymerization is not particularly limited, but is usually carried out by slurry polymerization in a hydrocarbon solvent. The hydrocarbon solvent used at this time is appropriately selected. For example, the hydrocarbon solvent used at the time of the above-mentioned contact is suitably used. The pre-polymerization catalyst may be used as a slurry after the completion of the pre-polymerization, or may be used, if necessary, after washing and drying to obtain a powder. At this time, the drying conditions are not particularly limited, but preferably the drying is performed at 0 ° C. to 100 ° C. under reduced pressure or under a flow of a dry inert gas.

The catalyst of the present invention is used for the polymerization of α-olefins. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, and 4-methyl-olefin. Examples thereof include vinylcycloalkanes such as 1-pentene and vinylcyclohexane, ethylidene norbornene derivatives, styrene and styrene derivatives, and include homopolymerization and copolymerization with these monomers. The polymerization process is not particularly limited, for example, it can be used in a gas phase polymerization method, a slurry polymerization method, a solution polymerization method, or a high-pressure polymerization method, but when the present catalyst is used, the bulk density is high, Since a polymer having a good particle shape can be obtained, it is suitably used for a gas phase polymerization method and a slurry polymerization method.

[0045]

According to the present invention, an olefin can be polymerized with high polymerization activity, and an olefin polymer having a high molecular weight can be produced.

[0046]

EXAMPLES Example 1 (1) Preparation of Catalyst After a 200 mL flask equipped with a stirrer was purged with nitrogen,
2.0 g of zinc ion-exchange type synthetic mica granules (average particle size: 59 microns) dried in advance at 200 ° C. for 2 hours under reduced pressure;
Further, as a metallocene complex, bis (i-propylcyclopentadienyl) zirconium dichloride, 60.2
70 mL of a complex solution in which mg was dissolved in toluene was added at room temperature. After stirring for 10 minutes, heptane was added to adjust the total amount of the solvent to 200 mL to prepare a slurry catalyst. (2) Polymerization In a 1.0 L autoclave dried at 100 ° C. for 30 minutes in a nitrogen stream in advance, heptane 5 was added at room temperature.
00 mL, 1-hexene 30 mL, and 8.0 mL of the slurry catalyst prepared in the above (1) (80 m
mg), the temperature and the pressure of ethylene were increased to 65 ° C. and 7.0 kgf / cm ² -G, respectively, to stabilize the temperature and pressure in the polymerization tank. Then, a heptane solution of triethyl aluminum (triethyl aluminum 2
(Equivalent to 85 mg) was added to initiate polymerization.
The polymerization was carried out for 1.5 hours while maintaining the total pressure at 7.0 kgf / cm ² -G. After the completion of the polymerization, the reaction system was cooled, and after purging ethylene, a polyethylene slurry was extracted and filtered. The obtained polymer was dried at 100 ° C. for 12 hours to obtain 22.3 g of an ethylene / 1-hexene copolymer. Table 1 shows the results.

Example 2 A catalyst was prepared in the same manner as in Example 1, except that 68.6 mg of bis (cyclopentylcyclopentadienyl) zirconium dichloride was used instead of bis (i-propylcyclopentadienyl) zirconium dichloride. Polymerization and post-treatment were carried out to obtain 22.8 g of a polymer. Table 1 shows the results.

Comparative Example 1 In Example 1, bis (n-propyl) was replaced with bis (n-propylcyclopentadienyl) zirconium dichloride.
Catalyst preparation, polymerization and post-treatment were carried out in the same manner except for using 64.7 mg of butylcyclopentadienyl) zirconium dichloride to obtain 26.2 g of a polymer. Table 1 shows the results.

Comparative Example 2 A catalyst preparation, polymerization and post-treatment were conducted in the same manner as in Example 1 except that bis (methylcyclopentadienyl) zirconium dichloride was used instead of bis (i-propylcyclopentadienyl) zirconium dichloride. Do
28.5 g of polymer were obtained. Table 1 shows the results.

[0050]

[Table 1]

Example 3 (1) Preparation of Preliminary Polymerization Catalyst Heptane (0.700 L) was added to a 1.5 L autoclave dried at 80 ° C. for 2 hours under a stream of dry nitrogen, and the temperature was controlled at 30 ° C. with stirring. 10.0 g of granulated trivalent chromium ion-exchange type synthetic mica (average particle size: 55 μm) previously dried under reduced pressure for 2 hours at 200 ° C., and bis (i-propylcyclopentadienyl) zirconium dichloride as a metallocene complex; 0.30 g of a 96 mL toluene solution was added, pressurized with nitrogen to about 0.5 kg-G (gauge pressure), and then contacted at that temperature for 10 minutes. After the end of the contact, a heptane solution of triethylaluminum (triethylaluminum, equivalent to 1.1 g) was added, and then 60 ° C.
And contacted at that temperature for another 10 minutes. After the contact, nitrogen was purged until the internal pressure became 0.2 kg-G, and then ethylene was fed at 0.45 L / min. When the integrated ethylene feed amount became about 7 times the amount of ethylene charged with respect to the charged synthetic mica, the feed of ethylene was stopped, and then the inside ethylene was purged while cooling the autoclave to stop the polymerization. After purging, the contents were withdrawn from a withdrawal line at the bottom of the autoclave into a flask with a 2 L internal volume sufficiently purged with nitrogen. After standing and decanting the solvent, drying was performed at 70 ° C. for 2 hours under reduced pressure to obtain a prepolymerized catalyst.

(2) Polymerization In a 1.0 L autoclave made of stainless steel, which had been dried at 100 ° C. for 30 minutes in advance with flowing nitrogen, heptane 5 was added at room temperature.
00 mL, an amount equivalent to 0.03 g (0.24 g) of the prepolymerized catalyst produced in the above (1) as a clay mineral, and 1
-60 ml of butene were introduced. The temperature and ethylene pressure were increased to 65 ° C. and 22.0 kgf / cm ² -G, respectively. When the temperature and pressure are stabilized, a heptane solution of triethyl aluminum (triethyl aluminum 5
(Equivalent to 7 mg) was added to the polymerization system to initiate polymerization. The polymerization was carried out for 1.5 hours while maintaining the ethylene pressure at 22.0 kgf / cm ² -G. After the completion of the polymerization, the reaction system was cooled, and after purging ethylene, a polyethylene slurry was extracted and filtered. The obtained polymer was dried at 100 ° C. for 12 hours to obtain 25.7 g of an ethylene / 1-butene copolymer. Table 2 shows the results.

Comparative Example 3 (1) Preparation of Prepolymerized Catalyst The procedure of Example 3 was repeated except that bis (n-butylcyclopentadienyl) zirconium dichloride was used instead of bis (i-propylcyclopentadienyl) zirconium dichloride. It carried out similarly to (1). (2) Polymerization Using the prepolymerized catalyst produced in the above (1), polymerization was carried out in the same manner as (3) in Example 3. Table 2 summarizes the results.

Example 4 (1) Polymerization 100 g of dried sodium chloride was introduced into a 1.5 L autoclave made of stainless steel which had been sufficiently purged with nitrogen.
The temperature was raised to 50C. When the temperature was stabilized, a heptane solution of triethylaluminum (equivalent to 100 mg of triethylaluminum) and an amount (0.64 g) equivalent to 0.08 g of the prepolymerized catalyst produced in (1) of Example 3 as a clay mineral were introduced. After replacing the inside of the system with ethylene, the temperature and the pressure of ethylene were set to 80 ° C. and 7, respectively.
In 5 minutes, the pressure was raised to 0 kgf / cm ² -G to initiate polymerization. The polymerization was carried out at 85 ° C. for 2 hours while maintaining the ethylene pressure at 7.0 kgf / cm ² -G. After the completion of the polymerization, the polymer obtained by removing sodium chloride by washing with water was dried under reduced pressure at 50 ° C. for 6 hours at normal pressure and further at 80 ° C. for 3 hours to obtain 68.5 g of polyethylene. Table 2 shows the results.

Comparative Example 4 (1) Polymerization A prepolymerized catalyst prepared in Comparative Example 3 (1) was used instead of the prepolymerized catalyst prepared in Example 3 (1).
Polymerization was carried out in the same manner as in Example 4. Table 2 summarizes the results.

[0056]

[Table 2]

[Brief description of the drawings]

FIG. 1 is a flowchart for helping an understanding of the present invention.

Claims (6)

[Claims] 1. An α-olefin polymerization catalyst component obtained by combining the following component [A] and component [B]. [A] A metallocene transition metal compound represented by the following general formula [1]. (CpR ¹ ) ₂ MX ¹ X ² [1] (In the formula [1], Cp represents a cyclopentadienyl group, and R ¹ represents a secondary or tertiary silicon atom directly bonded to a Cp ring. A silicon-containing group having at least one of a secondary or tertiary amino group and a hydrocarbon group having 3 to 20 carbon atoms in which at least one of carbon atoms of the hydrocarbon group is not bonded to a hydrogen atom or bonded to one hydrogen atom Or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms in which at least one of carbon atoms is not bonded to a hydrogen atom or bonded to one hydrogen atom, and M is titanium, zirconium or hafnium. , X ¹ and X ² are independently a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, an amide group, or trifluoromethanesulfonyl, Shows a group.) [B] an ion exchangeable layered silicate 2. The α-olefin polymerization catalyst component according to claim ¹ , wherein R ^{1 of the} component (A) is represented by the following formula. (In the formula [1], R ¹ is a silicon-containing group having a secondary or tertiary silicon atom directly bonded to the Cp ring, a secondary or tertiary amino group, a secondary or tertiary directly bonded to the Cp ring. Or a branched hydrocarbon group having 3 to 20 carbon atoms having 1 to 20 carbon atoms, or having 1 to 20 carbon atoms having a carbon atom directly bonded to the Cp ring not bonded to a hydrogen atom or bonded to one hydrogen atom Is a halogen-containing hydrocarbon group.) 3. R of component [A]¹, X¹And X^TwoIs
The catalyst for α-olefin polymerization according to claim 1, which is represented by the following:
Medium component. (In the formula [1], R¹Is cyclic and directly
No carbon atoms forming a part of the ring with 3 carbon atoms
20 hydrocarbon groups or halogen-containing hydrocarbon groups, X
¹And X^TwoAre each independently a halogen atom and carbon number
1-20 hydrocarbon or amide groups. ) 4. 0.01 to 1000 g per 1 g of the component [B] in the presence of the catalyst component according to claim 1.
An α-olefin polymerization catalyst component obtained by prepolymerizing the α-olefin of the above. 5. An α-olefin polymerization catalyst comprising a combination of the catalyst component according to claim 1 and the following component [C]. ## STR2 ## in _{^{[C] R 2 a AlX 3}} 3-a [2] ( Formula [2], R ² is a hydrocarbon group having 1 to 20 carbon atoms, X ³ is a halogen atom, a hydrogen atom, an alkoxy group, or Represents an amide group, and a is a number satisfying 0 <a ≦ 3). 6. A method for polymerizing an α-olefin, comprising polymerizing an α-olefin in the presence of the catalyst according to claim 5.